Artificial mass and process for making same



Patented Apr. 14, 1931 omrso STATES HERBERT nonnntor VIENNA,

PATENT osslcs AUSTRIA, ASBIGNOB TO BECK, ROLLER & COMPANY, 01

DETROIT, MICHIGAN 7 ARTIFICIAL MASS AND PROCESS FQR MAKIIN'G SAME V NoDrawing. Application filed'llay 11, 1929, Serial No. 362,460, and inAustria August 8, 1927.

The present invention relates to a process for producing organic massesof more or less high molecular weight, which may be employed alone or incombination with filling materials as the basis of pressed articles, asbinding agents or for preparing varnishes and other coating or impregnatng agents and the like.

The process according to this invention consists in heating condensationproducts of low molecular Weight, obtained with the aidof alkalinecontact agents from such phenolic substances, which only possess twoparticularly reactive positions in the molecule and which, when heatedalone change into an infusible condition, to elevated temperaturestogether with any ester-like chemical substances. Thereaction is accomanied with the formation of water and is to e regarded as a condensationreaction.

As the particularly reactive positions in a phenol are to be regarded,as is known the two ortho and the para position to the phenolhydroxyl.One of these positions must therefore be occupied by a substituent.Examples of the latter are, a hydrocarbon radical (alkyl, aryl, aralkyl,hydroaromatic radical) or an oxalkyl radical or chlorine. Oth-' ersubstituents have proved to beless suit able. One or both of the metapositions may on occasion also be occupied. Thefollowing are examples ofa few easily obtainable phenolic bodies of this kind: 0- and p-cresol,certain xylenols, carvacrol, thymol, p-tertiary butyl phenol and amylphenol, p-benzyl phenol, as well as the corresponding derivatives of mcresol, guaiacol, 0-" and pchlorophenol, 0- and p-chloro-m-cresol etc.Derivatives of the dioxybenzenes, i. e. divalent mono-nucleur phenolicsubstances, are also suitable, the conditions however, are somewhat morecomplicated and not quite clear. As, moreover, the use of thesesubstances is lacking in economy they Wlll not be further discussed.

On the other hand the applicability of all those di-valent, di-nucleurphenolic substances, which are derivatives of the pp-d1-oxy-di-phenylmethane, is to be emphasized.

They are easily obtainable and result from the condensation of 2 mole ofphenols or certain homolo ues with 1 mol of a carbonyl compound with theaid of hydrochloric acid or, if possible, other acids. In the presentcase the most suitable phenol homologue is o-cresol, fromwhichdi-Q-cresylol methane, ethane, propane or butane, is obtained accordingto whether condensation has been effected w th formaldeh de and itshomolo ues or acetone and its omologues. Cyclic etones may also beemployed in which case, for example, di-o-cresylol cyclohexane ordi-ocresylol methylcyclohexane corresponding to the above compounds, areobtained. Phenol, however, may also be used as starting material and,for example, 2 atoms of chlorine be introduced as substituents, in thedi-phenylol compounds thus obtained. in all these cases di-nucleurdi-valent phenolic substances are obtained, all of which also onlypossess two reactive positions in the molecule.

It is to be observed that condensation prod-- ucts from phenolicsubstances with only one reactive position in'the molecule may also beemploys Their yield is, however, considerably less and the action only avery limited one, which is in agreement with the fact that, when heatedalone, they cannot be converted into the infusible state. Phenols ofthis kind are, for example, certain xylenols, pseudocumenol, creosol,chlor-o-crescl and chlor-p cresol.

aand ,B-naphtol behave in a surprising manner like the last mentionedphenols, although they actually belong to the first mentioned group. 4

-My invention' includes the discovery that where a substantially neutralester-like body is reacted with a condensation product oflow molecularweight obtained by alkaline condensation from an aldeh do and a phenolicbody, which phenolic bo y has atthe utmost two unsubstitutedparticularly reactivepo'si v tions, a smooth reaction mass may be ob--tained, as contrasted with a lumpy mass containing insoluble andinfusible particles, such as would result where phenols having all threeparticularly reactive stitutedare employed.

The condensation products obtained from positions unsuh:

' formaldehyde and phenols, in which all three a particularly reactivepositions are unoccupied, are, unsuitable for the process, because, onheating, they rapidly further condense in such a wa that insolublemasses of resin in coarse or ne condition are separated or that they atleast become permanently turbid.

The mechanism of the reaction doubtless is that the molecules of thecondensation product do not only react with one another with theformation of products of high molecular weight, but also with theester-like substance or with its components. The alcoholic hydroxylgroupsof the condensation product,

products. The full valueof the process, how- 1 .ever, is only reachedwhen the ester-like subvery advantageous in this sense. On one ofknownas very reactive, may bring about unions so that multivalent estercomponents may be in part formed. This possibility in conjunction withthe first mentioned reaction may lead-to the formation of indlvidualgela tinous or rubber-like infusible and insoluble masses. It is aknown-fact that, in the esterification of nearly equivalent quantities'of polybasic carboxylic acids with polyvalent alcohols, infusiblemasses result. Similarl the possible production in this case of gelatl-In the present reaction also the gel formations appear to be due to thesame cause.

In general all possible ester-like substances have proved to beapplicable to the reaction. Even low molecular completely crystalloidesters, for example benzoic acid esters of mono-valent alcohols, yieldaccording to the proportions employed, thin to highly viscous oils orgelatinous masses. Estersof monovalent alcohols with polyvalentcomponents may yield, even with lesser quantities of the samecondensation product, gelatinous end stance is one which is not easilyvolatilized or better is practically non-volatile. Thus products, whichhave been obtained by esterification on both sides of a suitable mixtureof polyvalent and mono-valent components are the two sides, only apolyvalent component can suitably be represented. When suitableproportions are employed such ester-like substances are-fsoluble andfarfrom a rubberlike infusible condition. Under certain cir+cumstan'cesfeven small quantities of a condensation productproducetheabove described effect. p

The present process enables the proportions 'in the later stages of theprocess, they beof ester components to be replaced to a veryconsiderable extent 12;} the usually cheap mono-basic acid. The al endproduct, however, shows technically very similar properties to those ofan ester with a comparatively high proportion of the usually expensivepolybasic acid. The economic advantage of the process is thus, veryevident, the more so as at the same time a considerable saving inpolyvalent alcohol is also efl'ected.

It is, moreover, not necessar to start with the individual components 0the esters as such, it is also possible to replace the monobasic acids(for examplehigher fatty acids etc.) more "or less by their glycerides(i. e. fat or fatty .oil), in which case individual esters arenevertheless obtained apparently owing to re-esterification. In any casewhen they react with the condensation products have as though they hadbeen directly obtained. *Purely physical mixtures of complicated estersof this kind and ordinary fatty acid glycerides etc. may .of' coursealso be subjected together to the reaction with the condensationproducts. In cases such as these the economic advantage is, of course,still greater.

The mono-basic as well as thepoly-basic acids may be aliphatic,saturated or unsaturated, aromatic or hydroaromatic, they may or may notcontain alcoholic or phenolic hydroxyl groups v(i. e. they may or maynot be oxy acids). Glycerine is the most important example of apolyvalent alcohol, alcohols of higher valency or the only di-valentglycol may, however, also be employed.

Finally it should be again emphasized that estersfof every kind may beemployed forihe reaction. .The hydroxyl compound may also be algphenoland the acid an inorganic acid.

A condition for the success of the reactionis merely that thecondensation product, which at elevated temperature first gives off itsmechanically combined water, is then 0 soluble in the ester-likesubstance (at least when hot) before a condensation reaction takes placeas otherwise, of course, no mutual reaction can result. This result isobtained by suitably choosing the substituents' in the 1 phenolicsubstance. It may in some cases be convenient for instance if theester-like compound is per se a resin-like substance of high meltingpoint to carry out the process in the presence of a suitable solvent;the latter may, no if required, be removed by distillation when thereaction is over.

The preparation of the condensation products is effected in-knownmanner, preferably by leaving the'fphenolic substance'or a mix- 1-25ture of several phenols and aqueous formaldehyde together with at leastso much. alkali hydroxide, that a clear solution results, if-.necessarywith the aid of alcohol, to react-for a long vtiiiie at room temperatureor slightly elevated temperature. The resulting reaction product is thenprecipitated with-acid-reactin agents. Formaldehyde in excess of theequimolecular quantity is with advantage em loyed. The above escribedeffect may be utilized in different ways. The quantity of condensationproduct employed may be such that, if the condensation reaction with theester were carried to completion an insoluble, rubber-like rod'uct wouldresult,'in which case the reaction must be interrupted beforecompletion, if necessary even in its initial stage. n this case thesolutions of the resulting products yield coatings, which becomeparticularly hard at furnace temperatures. If necessary, siccatives mayalso be added to the reaction product. Products of this kind resultingfrom an interru ted reaction are also particularly suitable for use asplastic masses. They may be employed with or without filling materialsfor the preparation of various commodities.

An alternative procedure is to employ the condensation product in such aquantity that even on complete condensation with theesterlike product anoily, possibly resin-like or wax-like end product is obtained, whichmore or less approaches the rubber-like condition without actuallyattainin it. An increase of the colloidal condition is at leasteffected. In the case of solid, particularlyresin-like esters, anincrease of their melting point is. as a rule, effected as well. Theheating of the product can in this case be carried to about 200-220 O.for any desired time without any noteworthy increase of the. colloidalvcondition being observed. The still soluble products or their solutionsmay be employed alone as the basis for paints or, in general,

as raw materials for the production of var-.

nishes and other coating masses. If the acid components or one of thecomponents is derived from dryin or semi-drying oils or from fatty oilsw ich only thicken by the absorption of'oxygen, a siccative may also.

be added and in this way, tough and hard dr ing varnishes may beobtained.

11 individual cases very special effects may also be obtained. by meansof the .process. Thus for example, wood oil, even when condensed withonly a small quantity of a suitable condensation pro-duct, loses itsknown disadvantageous manner of drying. A particularly ,hard, smooth andrapidly drying varnish may in fact be obtained inthis way. I

' Ewamplea I v 6 parts of melissic palmitate (beeswax) are. melted andstirred up. with the liquid condensation product obtained from one partof p-tertiary-amyl 'phenol and one part of 30% formaldehyde. Thetemperature is then gradually raised to 240 C". The brown properties ofthe pro whic differ from these of the bees wax ita self. It is hardermore easily polished, more plastic and in thin layers more transparentand when cured out in thin plates 1s elastically pliab e. When pouredonto a smooth surface it displays considerable adhesive powers. Ingeneral the colloidal not are considerably increased, and the productitself to a certain extent assumes resin-like ro erties.

2. 4 arts of melted bee ta low are stirred the viscous condensationproduct resulting from 1 part of p-tertiar -butyl-mcres ol andl part offormaldehy e.40% by volume. gradually heated up to 190 C. and

maintained for 14 A, hours at this temperature. The end product has thecharacter of a very viscous oil and only sets when cooled with ice to alard-like mass.

3. 100 grms. of castor oil and the crystal line condensation productobtained from 40 grms. of p-cresol and 60 grms. of 30% formaldehyde areheated with stirring up to 180 C. and maintained at this temperatureuntil a cooled sample shows rubber-like elastic properties. The productissoluble in benzene and benzene-alcohol mixtures, as well as in variousother solvents, but not in alcohol alone. 'When mixed witha' siccative avarnish is obtained which on drying. becomes considerably hard. Theproduct may also'be added as a softener to othersiccative-freevarnishes.

4. The thick oily condensation product obtained with the aid of alkalifrom 1 part of p-tertiary-butyl phenol and 1 part of 30% formaldehyde byheating for 24 hours to 50-55 C. and precipitated with acids isintroduced at about 130 G. into 10 partsof wood oil with stirring. Thetemperature is then gradually raised-to 220 C. The end product has theviscosity of a caster oil and yields with a suitable quantity ofsiccative and on suitable dilution a varnish of excelent propertieswhich dries clear extremely rapidly.

5. A viscous condensation product obof thymol and 40 grms. of 30%formaldehyde is introduced into and dissolved in 500 grms. of amoderately boiled mixture of wood oil and linseed oil. This mixture, socalled honey-oil is prepared in the usual manner by heating a mixture of1 part of wood oil and 3 parts'of linseed oil for 4 hours at 280 C. Itis to be regarded as the lmixed glycerine ester of mono-basic olefinecarboxylic acids and poly-basic olefine carboigylic acids obtained bypartial polymerization. The temperature is'gradually raised whilststirring. After expelling the mechanically combined water the reactionmixture is clear even when cold. It is finally heated up to 220 C. Theproduct is still tained with the aid of alkali from 30 grms.

soluble and when cold represents a sticky mass. Onadding a siccative andvery rop cl and tough drying varnish is to 160200 C. atenacious adhesivecoat sorbing oxygen from the air yields on heating etc. For this process1 hour to 10 minutes are required according to-the temperature employed.With the addition of sicccatives a coat of pre-eminent hardness andresisting power is obtained at this temperature.

6. A condensation productof low molecular weight obtained from 7 0 grms.of o-cresol and 100 grms. of 30% formaldehyde is dissolved with heatingin 200 grms. of tricresyl phosphate and the 'xture heated to 160 C.until a sample on coo in shows a highly viscous ropy oil. It is solu lein benzene hydrocarbons and other solvents. It maybe employed, forexample, as the basis for furnacedryin varnishes. On continued heatingof 160 or higher a rubber-like to wood oil gelatinous mass is obtained.

' 7.100 s. of succinic acid, 150 grms. of lactic acid (100%) and 120grms. of glycerine (98%) are heated to 160.200 C. until a softresin-like product with an acid number of about 25 is obtained. At about100120 G. the crystalline condensation product obtained from grms. ofp-chlorophenol and 35 ms. of 30% formaldehyde is introduced anxf soongoes into solution. The temperature is gradually raised to 220 C. A softresin having rubber-like elastic properties which is completely solublein acetone and alcohol-benzene mixtures is obtained.

8. A condensation product resulting from grms. of p-cblor-m-cresol andgrms.

of formaldehyde (40% by Volume) is added with heating to the fairly hardand brittle resin-like esterification product prepared as in example 7from 100 grms. of succinic acid, 160 grms. ofsalicyclic acid and 100grms. of glycerine and the mixture caused to react by raising thetemperature to about 200 C. Without an apparent increase in the meltingpoint of the resin-like product being ob. served a resin of markedshellac-like properties is obtained. The resin-like condition in thiscase is without doubt very considerably increased. The product issoluble in acetone and other solvents and may be employed for preparingpolishes and the like. Its solu- ;--tions may further be mixed with bothnitrocellulose and with acetylcellulose varnishes. In both cases clearsatisfactorily adhering films are obtained.

9. The ester-like semi-liquid reaction prod-- not obta ned from 150grms. of citric acid (crystalhne), 100 of ricinoleic acid 100 grms. ofsahcy 0 acid and 115 grms. of

- glycerine on the one hand and 45 grms. of

10. The condensation product obtained as so in Example 6 is condensedwith the thick oily ester obtained from 100 grms. of. phthahc anhydride,100 rms. of oleic acid and 65 grms. of ethylene g ycol. A soft,rubber-likef elastic resin is obtained, which is soluble in benzenehydrocarbons as well as other solvents and is very suitable as an addition to nitrocellulose varnishes.

11. The condensation product resulting from 3 artsof xylenol (1 :4: 5)and 4 parts 6 of 30% orrnaldehyde is added to an ester having an acidnumber of 30 and obtained from 6 parts of d-tartaric acid, 4-parts ofbenzoicacid and 4 parts ofethylene glycol. A soft soluble resin, whichis elastic-like rubber, is obtained as in Example 10. 12. 4 parts ofphthalic anhydride, 6 parts stearic acid and 3 parts of glycerine areesterified together at 180-220 C. until an acid number of about 20 isreached. The product rapidly sets at room temperature to a cloudywax-like mass, which is somewhat sticky to the touch. The wax-likecharacter is alsomanifested in its solutions, which,

whenpoured out in thin layers, allow the V solvent to evaporate veryslowly.

of o-cresol and 20 grms. of; methyl-ethyl-ketone are condensed with theaid-of concentrated hydrochloric acid (37%). The reaction product is amixture of o-cresol and di-o-cresylol-butane. It is condensed at roomtemperature with 100 grms. of formaldehyde (40% by volume) with the aidof caustic soda and the condensation prodiict precipitated with acidafter about two weeks 300 grms. of the ester-like product and half ofthe condensation product obtained above are heated together to 230 C.The resulting product represents at about 35 C. a soft elasticresin-like transparent mass. Even on cooling to room temperature it isfirst clear and elastically flexible. After a few hours it merelybecomes translucent and is then fairly brittle and easily friable. It issoluble in benzene hydrocarbons. Its'solutions, when poured out in thinlayers, allow the solvent easily to evaporate. The layer of productwhich remains is first clear, but after some time becomes cloudy likewax and possesses lar to those of the end pro to a high degree the powerof repelling water.

131. 220 grms. of the ester-like product obtained as in Example 12 areheated to 150 C. with the remaining half of the condensation productobtained in the same example, until a cooled sample shows dpropertiessimiuct obtained in Example 12. The product like the latter is soluble,inv benzene and-the "like. a The, solutions yield a temporarilyclearfillIlyWhlCll may be hardened at 150-200 G. and which adheres well tothe coated surface, possesses strong water-repelling powers and remainspermanently clear. The product itself, mixed with filling agents of anykind, may be employed for preparing compressed substances. 14. The esterof acid number 10 obtained from 50 grms. of sebacic acid, 100 grins. oftechnical abietic acid and grms. of glyc-v erine and which represents asoft sticky resinous mass, is worked up in the usual manner with thecrystalline oily condensation product obtained from 13 grms. of guaiacoland 18 grms. of 30% formaldehyde; A resin somewhat softer than shellacis obtained, which,

.at the temperature of its melting point, is

elastic like rubber. It is. soluble in benzene hydrocarbons, acetoneetc., and miscible to a clear solution with'nitrocellulose in anyproportion.

15. 2 parts of o-cresol and 1 part of technical methyl-cyclohexanone arecondensed with the aid of hydrochloric acid. Thereaction productconsists of three isomers of di- '0-cresylol-methyl-cyclohexanonecinema, -(on,.c.H,cH

and represents a thick oily mass permeated with separated crystals. Itis condensed by means of caustic alkali at room temperature with 2 partsof formaldehyde (40% by volume) and the thick oily condensation productthen separated with acids.

The latter is worked up with 15 parts of an ester obtained from 100grms. of camphoric acid, 250 grms. of abietic acid and 65 grins. ofglycerine and which represents a fairly brittle resin with an acidnumber of 20 and a melting point of 75-85 C. On condensing thelatter'witll the condensation product, a very hard resin melting about30 0. higher is obtained. By relatively increasing the condensationproduct a resin can be readily obtained, which is extremely hard and atthe temperature of its melting point represents a rubber-like elasticmass.

It issoluble in benzene hydrocarbons and yields clear films when mixedwith nitrocellulose.

16 (a).-76 grms. of benzyl chloride are slowly added with gentle heatingat thestart to 108 grms. of technical m-cresol containing 60% of purem-cresol. In the simultaneous presence of a catalyst consisting of about5 grins. of d zinc chloride the reaction starts airly uiet y and may, ifnecessary be later assists and brought to completion b heating. Thebenzyl group merely enters the m-cresol as a substituent with theremoval of 1101, most probably in the para position ossibly also in theortho position. According to the work of Beilstein, the position of thebenzyl group is not known. The p-cresol apparentl remains untouched. Theoily reaction'pro not is repeatedly washed with hydrochloricacid-containing water and then 180 grms. of 30% formaldehyde addedtogether with so much caustic alkali that after shaking clear solutionresults. After about 2 weeks the condensation product is precipitated.

(b) 250 grms. of alcohol-soluble manila are melted at 230240 C. with1000 grins. of colophony and, if necessary, the melt freed from dirtparticles by filtration through a fine sieve. The mixture is thenesterified at a temperature of 24.0280 C. with 150 grins. of glycerine(sp. g. 1.23).

Manila copal contains polybasic resin acids. 7

The condensation product is gradually introduced at 170 G. into thismixed ester and the temperature then raised to 250- C. The end productis hard and tough and readily soluble in drying oils.

17. The thick oily esterification product obtained from a parts ofphthalic anhydride, 6 parts of linoleic acid, 2 parts of colophony and 3parts of glycerine are heated to 150 C. with the condensation productobtained from 2 parts of butyl phenol and 2 parts of 30% formaldehydeuntil a sample when cold represents a soft rubber-like elastic mass. Theproduct is not only soluble in benzene hydrocarbons, but also in oil ofturpentine and mineral spirits and yields, with or without the additionof siccatives, a varnish which dries very hard at furnace temperature.

4-5 parts of linoleic acid employed for y again the above ester may bereplaced by linseed oil. lit only takes considerably longer until auniformly clear reaction mass is formed.

18. The thick oily esterification product The mixture of phenolicsubstances is-obtained by chlorinating the m-cresol dissolved in glacialacetic acid with the calculated quantity of elementar chlorine with icecooling, and consist mamly of the para compound.

The end product is very soft and elastic like rubber, it may be dilutedto a limited extent with alcohol, in any .pro ortion with benzenehydrocarbons and ester- 'ke solvents resulting from 50 ms. *of .di-cOlkdiphenylol-propane an 60. of 30% formaldehyde. Aresin-like vr'oduct,some-- what softer than shellac,-'.resu ts, which, like thelatter, has rubber-like elastic-properties at the temperature of itsmelting point. It can with advantage be employed as a resin fornitrocellulose varnishes. I

20. 105 grms. of crystallized citric acid 200 grms. of benzyl alcoholare heated together in a distillation flask until a temperature of 250?C. is reached. The benzyl'alcohol distilled over with the water ofcrystallization and reaction is separated therefrom, re-introduced intothe flask the above described operation being then repeated. Finally theunchanged'benzyl alcohol is removed by applying a vacuum. The reactionprodnot, which remains in the flask amounts to about 135 grms. and hasan acid number of 90-100; about 25 grms. of water are collected in thereceiver. That means that one carboxylic groupwhas been esterified andpartial formation of anhydride has taken lace. 50 grms. of oleic acidand 42 grms. ofg ycerinc are now added and the whole isheated to 250v C.untilan acid number of 10 is reached. The light brown product is a thickliquid having the consistency of a thick boiled linseed oil. v Y

The condensation product obtained, as described in Example 18 isincorporated at a temperature below 140 C. the temperature being thengradually raised up to 220 C. The final product is a resin, which issoft at ordinary temperature, of rubber-like elasticity, soluble inbenzene hydrocarbons, esterlike solvents and so on, and may be added tonitrocellulose varnishes in anydesired proportion The formation ofcondensation products which is caused by the interaction of resins oflow acid number with phenol formaldehyde condensation products, in whichthe para position of the phenol is occupied by a hydrocarbon residue asdescribed in my copending application Ser. No.- 218,587 is not claimedspecifically in the present application.

in the following, claims the expression soluble artificial masses isintended to designate bases for coatings of all kinds, particularlyvarnishes, and bases for impregnating agents, binders and for allsortsof com m odities.

of glycerine is heated to ,140-' 200 0. together with a condensationroduct.

ea ers.

The acids and-.their'anhydridesare to be. considered as equivalent informing the This .a plication is a continuation in part of my ifs;application Serial No. 218,587. What I claim is:--

L-Aprocess of making a soluble artificial mass, which comprises causinto react a substantially neutral ester-like od not rendered-infusiblebyabsolute-esteri cation, by heating said ester-like body with anon-resin- "like condensation' product of comparatively low molecularweight obtained by alkaline condensation from ormaldehyde and a phee.nolic body, which phenolic body has at the utmost two-:unsubstituted{particularly reactive positions, the said ester-like body being used ina substantial quantity'as one of the main ingredients in the reaction.

2. A'process of making a soluble artificial mass, which comprisescausing to react a substantially neutral ester-like body not renderedinfusible by absolute-esterification, by j heating said ester-like bodywith a non-resinlike condensation product of comparatively low molecularweight obtained-by alkaline condensation from formaldehyde and aphenolic body, which phenolic body has at the utmost two unsubstitutedparticularly re--- active positions, the said ester-like body being usedin greater roportions than the said phenol. formaldehy e condensationproduct. 3. A process accordin to claim 1in which the ester-likesubstance. as radicles of both monovalent and polyvalent groups.

4. A process according to claim 1 in which the ester-like substance hasacid radicles derived from a natural gylceride of an unsaturated fattyoil, and in which process a drier is added to the reaction product.

5. A soluble artificial mass produced according to claim 1.

6. A soluble artificial mass produced according to claim 2.

7. A process according to claim 1 in which the ester-like substance hasacid radicles derived from a natural glyceride for an unsaturated fattyoil. In testimony whereof I aflix my signature.

HERBERT HONEL.

